Process for basic sulfurized metal phenates



United States Patent Ofiice 3,178,368 PRGCESS FOR BASIC SULFURIZED METAPHENATES Walter W. Hannernan, El Cerrito, Califi, assignor to CaliforniaResearch Corporation, San Francisco, Cahfi,

a corporation of Delaware No Drawing. Filed May 15, 1962, Ser. No.194,996

. 5 tilaims. (Cl. 252--33.4)

This invention pertains to a new process whereby highly basic sulfurizedmetal phenates are prepared. In particular, this process pertains to themanufacture of overbased sulfurized alkaline earth metal alkyl phenates.

Basic sulfurized alkaline earth metal alkyl phenates are used ascompounding agents in lubricating oils to neutralize harmful acids, toinhibit corrosion, piston ring sticking and gum formation in internalcombustion engines resulting from oxidation of the lubricating oil andoxidation polymerization of the engine fuel residues.

For many years, metal salts of phenolic materials have been used asadditives for mineral lubricating oil compositions used in thelubrication of internal combustion engines. In combination with numerousother additives, the metal phenates improve the detergencycharacteristics of the lubricating oil, reduce engine wear, minimize theformation of harmful deposits 011 engine parts, and improve theresistance of the oil to oxidation.

Numerous attempts have been made to prepare oilsoluble sulfurize-dalkaline earth metal alkyl phenates which have the detergentcharacteristics of the metal phenates, and, in addition thereto, theproperty of neutralizing larger amounts of acidic bodies than possiblewith the presently available normal or basic sulfurized alkaline earthmetal phenates. By the particular process described herein, it ispossible to prepare overbased sulfurized alkaline earth metal alkylphenates which can neutralize large amounts of acidity than possiblewith phenates available heretofore.

By the use of the term herein, normal sulfurized alkaline earth metalphenates refer to the metal phenates wherein the mole ratio of metal tothe phenol nucleus is about 1:2, such as wherein R represents the alkylsubstituent radicals on the benzene ring, and M is an alkaline earthmetal. The sulfur (S) is attached to both of the benzene rings.

The term basic carbonated. sulfurized alkaline earth metal phenatesrefers to su-lfurizcd alkaline. earth metal phenates having base ratiosin excess of 1.2; that is, the percent of the total alkaline earth metalto the metal of the normal phenate is greater than 20% in excess of themetal of the normal sulfurizecl alkaline earth metal phenates. A metalphenate having a base ratio of 1 is a neutral (a normal) phenate.

It is a particular advantage of this invention, that by the processdescribed, basic carbonated sulfurized alka line earth metalphenateshaving metal contents greater than 20% in excess of the metalpresent in the corresponding sulfurized normal alkaline earth metalphenates can be prepared. In particular, the base ratios of theresulting basic phenates have values from 1.2 to 4.5 or higher.

The overbased carbonated sulfurized alkaline earth metal phenatesdescribed herein are particularly useful when incorporated inlubricating oil compositions for diesel engines.

It is a primary object of this'invention to set forth a new method ofpreparing highly over-based carbonated sulfurized alkaline earth metalphenates.

3,l?8,3t8 Patented Apr. 13, 1965 In accordance with this invention, ithas been discovered that oil-soluble overbased carbonated sulfurizedalkaline earth metal phenates can be prepared by the reaction of alkylphenols with alkaline earth metal oxides or hydroxides, followed bycarbonation with CO in the presence of glycol, sulfonates, and a highmolecular weight alcohol. It is essential to the process describedherein that the reaction mixture contains (1) a sulfonate, (2) ethyleneglycol, and (3) a high molecular weight alcohol. Furthermore, for thesatisfactory use as a lubricating oil additive of the final overbasedsulfurized alkaline earth metal phenates, it is essential that the finalbasic phenateoil blend contain the sulfonate, and it is desirable thatthe final oil blend contains a portion of the high molecular weightalcohol.

Briefly, the process of this invention comprises blending, then heatingwith agitation, a mixture of an alkyl phenol, a sulfonate, a highmolecular weight alcohol, lubricating oil, and sulfur. Hydrated lime (orCaO) is then added to this blend. The mixture is then heated, andethylene glycol is added. Water of reaction is removed; the mixture iscooled, and carbon dioxide is added. Uncombined CO is removethand thereaction vesesl is heated to remove ethylene glycol, water, and highmolecular weight alcohol.

Alkyl phenols which are usedherein in the reaction mixture arerepresented by the formula:

wherein A is an essentially hydrocarbon aromatic radical, preferably abenzene radical, R is .a straight-chain or branched-chain, saturated orunsaturated essentially hydrocarbon radical having from 4 to 30 carbonatoms and a is a number having a value from 1 to 2. The total number ofcarbon atoms for R has a minimum value of 8. Thus, when a is 1, theminimum number of carbon atoms in R is 8.

Examples of suitable hydrocarbonaceous radicals include alkyl radicals,such as butyl, hexyl, octyl, decyl, dodecyl, hexadecyl, eicosyl,tricontyl radicals; radicals derived from petroleum hydrocarbons, suchas white oil, Wax, olefin polymers (e.g., polypropylene andpolybutylene) etc. i

The basic sulfonates used herein contain from 0% to 300% of metal inexcess of the metal of normal sulfonates, that is, essentially neutral,metal sulfonates. The basic sulfonates used herein are derived fromneutral sulfonates represented by the formula:

wherein R is a high molecular weight straight-chained or branched-chainsaturated or unsaturated essentially hydrocarbonaceous radical having amolecular weight of about to about 800; A is an aromatic radical, suchas benzene, naphthalene, anthracene, etc; a isa number having the valueof 1 to 4; and M is an alkaline earth metal.

As the metal, the term alkaline earth metals, includes preferablycalcium, barium, and strontium; calcium is particularly preferred. Y

Examples of suitable hydrocarbonaceous radicals are the following:dodecane, hexadecane, eicosane, triacontane radicals; radicals derivedfrom petroleum hydrocarbons such as white oil, wax, olefin polymers(e.g., polypropyleneand polybutylene, etc.). The sulfonic acids used inpreparing the basic sulfonates of this invention also include theoil-soluble sulfonic acids obtained from petroleum, such as the mahoganyacids, and the synthetic sulfonic acids prepared by various methods ofsynthesis (e.g., sulfonic' acids prepared by reacting a chlorinatedwhite oil with benzene, using hydrofluoric acid as the catalyst, thentreating the resulting white oil alkylated benzene with chlorosulfonicacid or fuming sulfuric acid to form a white oil benzene sulfonic acid).

The metal sulfonates are exemplified as follows: calcium white oilbenzene sulfonate, barium white oil benzene sulfonate, calciumdipolypropylene benzene sulfonate, barium dipolypropylene benzenesulfonate, calcium mahogany petroleum sulfonate, barium mahoganypetroleum sulfonate, calcium triacontyl benzene sulfonate, bariumtriacontyl benzene, etc.

The high molecular weight alcohol, which is used in amounts no more than75% by weight of the alkyl phenol charged, preferably 10% to 50%, arethose monohydric alcohols containing from 8 to 18 carbon atoms. Thesealcohols are exemplified as follows: octyl alcohol, decyl alcohol,dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, cetyl alcohol,etc.

In the process described herein, a lubricating oil may be used as areaction medium. Thus, by such use of a lubricating oil, oilconcentrates of the desired highly basic carbonated sulfurized metalphenates can be obtained. Such lubricating oils include a wide varietyof lubricating oils, such as naphthenic base, paraffin base and mixedbase lubricating oils, other hydrocarbon lubricants, e.g., lubricatingoils derived from coal products and the synthetic oils, e.g., alkylenepolymers (such as polymers of propylene, butylene, etc., and themixtures thereof); alkylene oxide type polymers, e.g., alkylene oxidepolymers prepared by polymerizing the alkylene oxides, e.g., propyleneoxide, etc., in the presence of water or alcohols (e.g., ethyl alcohol);carboxylic acid esters, for example, those which are prepared byesterifying such carboxylic acids as adipic acid, azelaic acid, subaricacid, sebacic acid, alkenyl succinic acid, fumaric acid, maleic acid,etc. with alcohols such as'butyl alcohol, hexyl alcohol, 2-ethylhexylalcohol, and pentaerythritol; alkyl bcnzenes, polyphenyls; polymers ofsilicon; etc.

The several components which are used in this process are used incertain proportions with respect to each other. For each molal quantityof alkyl phenol, it is desirable to use from 0.01 mole to 1 mole ofsulfonate, preferably 0.01 mole to 0.05 mole, and from 0.1 mole to 1.5mole of high molecular weight alcohol, preferably tridecyl alcohol.

The amount of elemental sulfur present in the reaction mixture is suchthat the mol ratio of sulfur to alkaline earth metal of the basicsubstance is from 0.25 to 4.0. It is preferred that the mol ratio is inthe range of 0.5 to 1.5.

The amount of alkaline earth metal oxide or hydroxide which is used isthat amount which will be sufficient to give a base ratio of 1.2 to 4.5,preferably 1.5 to 3.5. The amount of alkaline earth metal oxides orhydroxide used in the reaction depends on the amount of metal desired inthe product in excess of that of the normal phenate. Normally, in thepreparation of basic carbonated sulfurized phenates a slight excess(e.g., 5 mole percent excess) of calcium oxide or hydroxide is used inthe reaction mixture over that desired in the final basic phenateproduct.

The carbon dioxide used is from 300 mole percent to mole percent,preferably 150 mole percent to 10 mole percent of the alkyl phenolcharged.

In the process of this invention, it is preferred to use ethyleneglycol. The amount of glycol used will depend upon the amount of calciumoxide or hydroxide used.

A sufiicient amount of glycol is employed to bring the reactants intoefficient contact for substantial reaction in a reasonably short time;that is, the amount of glycol used is sufiicient to dissolve a portionof each of the reactants and to cause substantial contact between saidreactants. For this purpose it is beneficial to use certain ratios byweight of the alkaline earth metal oxide or hydroxide to glycol. Thealkaline earth metal-glycol mole ratio may vary from 2 to 1 to about0.25 to 1.0; preferably from 1 to 1 to about 0.5 to 1. i

According to the process described herein, there is first formed a blendconsisting of an alkyl phenol, a sulfonate, a high molecular weightalcohol, and an oil of lubricating viscosity. This mixture is thenheated with agitation to temperatures from 150 F. to 190 F., followed bythe addition of the sulfur and calcium hydroxide (or oxide). Ths blendis then heated to temperatures in the range of 250 F. to 300 F., andthat temperature is maintained while ethylene glycol is slowly added.The water of reaction liberated after the addition of the glycol is thenremoved by heating to temperatures of about 340 F. The reaction mixtureis cooled slightly, followed by carbonation by means of carbon dioxideat temperatures from 250 F. to 350 F. Any uncombined CO is then removed.The reaction blend is then heated for 2 to 10 hours at temperaturesranging from 300 F. to 390 F., during which heating the absolutepressure is reduced to 4050 mm. Hg to remove glycol. In certaininstances, some of the high molecular Weight alcohols may be removedalong with the ethylene glycol. However, whether or not any or all ofthe high molecular weight alcohol is removed, the resulting lubricatingoil composition is highly effective for its intended purpose. When theparticularly preferred high molecular weight alcohol is used, that is,tridecyl alcohol, it is beneficial that at least 50%, by weight, remainin the lubricating oil composition. However, with this preferredalcohol, the final lubricating oil composition may contain from 30% to50%, by weight, of the original charge of the tridecyl alcohol. Thus,the high molecular weight alcohol may be removed in its entirety oramounts up to of the initial charge may remain in the final composition.

The examples hereinbelow illustrate the process of this invention.

EXAMPLE I Preparation of basic sulfurized carbonated calcium alkylphenate A mixture of 4,170 pounds of an alkyl phenol having a hydroxylnumber of 184 wherein the alkyl radical was derived from a polypropylenehaving an average of 12 carbon atoms, 508 gallons of a Californiarefined base oil having viscosities of SSU at 100 F., 436 pounds of abasic calcium sulfonate containing 40% calcium in excess of that amountfor a neutral sulfonate (i.e., the base ratio was 1.421), and 1294pounds of tridecyl alcohol was heated to F. with agitation. Sulfur, 854pounds, was charged to the vessel with the temperature maintained at180-190 F. Hydrated lime, 1974 pounds, was added to the blend. Thetemperature of the reaction mixture was increased to 260 F. Unheatedethylene glycol, 134 gallons, was added slowly to the reaction mixture,which was kept at a temperature of 260-270 F. for the glycol addition.The reaction mixture was then heated to 340 F. to remove water.

With rapid agitation of the reaction mixture 574 pounds of CO was addedat a rate of 100 pounds per hour at an initial temperature of 330 F.Uncombined CO was removed. The mixture was heated to 390 F. at anabsolute pressure of approximately 40 mm. Hg to remove, by distillation,water, ethylene glycol, and tridecyl alcohol. The remaining lubricatingoil blend contained 9.72%, by weight, calcium.

As noted hereinabove, it is desirable that the final lubricating oilcomposition have a high basicity. In the process described, it isdesirable that the initial amount of alkyl phenol be from 20% to 45%, byWeight, based on the final composition, preferably from 25% to 35%, byweight. The lubricating oil reaction medium is used in amounts from 15%to 50%, by weight, based on the finished composition, preferably from20% to 30%, by weight.

The metal sulfonate used in the example hereinabove was a concentrateconsisting of 46.4% by weight of a mineral lubricating oil and 53.6% byweight of a calcium petroleum sulfonate wherein the petroleum radicalwas derived from a mineral oil having a viscosity of 500 SSU at 100 F.The calcium content of the oil concentrate was 11.4% by weight, and thebase ratio was 1.4.

I claim:

1. A process of preparing sulfurized basic alkaline earth metalcarbonated alkyl phenate comprising forming a blend comprising apetroleum lubricating oil, an alkyl phenol wherein said alkyl radicalhas from 4 to 30 carbon atoms and the total number of carbon atoms inthe alkyl groups is at least 8, an alkaline earth metal alkyl arylsulfonate in an amount of from 0.01 to 1 mol per mol of said alkylphenol and an aliphatic saturated monohydric alcohol having from 8 to 18carbon atoms in an amount of from to 75% by weight of said alkyl phenol,heating said blend to temperatures in the range of 150 F. to 190 F.,adding thereto a basic substance selected from the group consisting ofalkaline earth metal hydroxide and alkaline earth metal oxide in amountnecessary to give a base ratio of from 1.2 to 4.5 for said basicalkaline earth metal carbonated alkyl phenate, and sulfur in an ofsulfur to basic substance has a value from 0.25 to 4, heating said blendto temperatures in the range of 250 F. to 300 F., and at thattemperature, adding unheated ethylene glycol thereto in amount such thatthe mole ratio of basicsubstance to ethylene glycol is from about 2:1 toabout 0.25:1, removing the resulting Water of reaction by heating totemperatures of about 340 F while maintaining temperatures no lower than250 adding carbon dioxide 300 mol percent of temperature of the reactionmixture at temperatures of 3100 F. to 390 F. at reduced pressure toremove ethylene g ycol.

2. A process of preparing a sulfurized basic alkaline earth metalcarbonated alkyl phenate comprising forming a blend comprising apetroleum lubricating oil, an alkyl phenol wherein said alkyl radical isderived from a polypropylene having an average of 12 carbon atoms, analkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1mol per mol of said alkyl phenol, an aliphatic saturated monohydricalcohol having from 8 to 18 carbon atoms in amount of from 10% to 75% byweight of said alkyl phenol, heating with agitation to 130 F., whilemaintaining temperatures in the range of 180 to 190 F., adding thereto abasic substance selected from the group consisting of alkaline earthmetal hy droxide and alkaline earth metal oxide in amount necessary togive a base ratio for the aforesaid carbonated alkylphenate of from 1.2to 4.5 and sulfur in an amount such that the mol ratio of sulfur toalkyl phenol has a value from 0.25 to 4, heating with agitation to 260F., and while maintaining the reaction mixture at temperatures of 260270R, adding unheated ethylene glycol thereto in amount such that the molratio of basic substance to ethylene glycol is from 2:1 to about 0.25:1,heating to a temperature of about 340 F. to remove Water of reaction,adding carbon dioxide in an amount of from 10 mol percent to 300 molpercent of said alkyl phenol, followed by heating to temperatures of 390F. at reduced pressure to remove ethylene glycol and at least 50% of theoriginal charge of said alcohol.

3. A process of preparing sulfurized basic alkaline earth metalcarbonated alkyl phenate comprising forming a blend comprising from 20%to 30% by weight, based on the final composition, of a petroleumlubricating oil, from 20% to 45% by Weight of an alkyl phenol whereinsaid alkyl radical has from 4 to 30 carbon atoms and the total number ofcarbon atoms in the alkyl groups is at least 8, an alkaline earth metalalkyl aryl sulfonate in an amount of from 0.01 to 1 mol per mol of saidalkyl phenol and an aliphatic saturated monohydric alcohol having from 8to 18 carbon atoms in an amount of from 10% to 75% by Weight of saidalkyl phenol,

F. in amount of 10 mol percent to said alkyl phenol, maintaining theamount such that the mol ratio ing said blend to temperatures in therange of 250 F.

to 300 F., and at that temperature, adding unheated ethylene glycolthereto in amount such that the mole ratio of basic substance toethylene glycol is from about 2:1 to about 0.25:1, removing theresulting water of reaction by heating to temperatures of about 340 F.,while maintaining temperatures no lower than 250 F. adding carbondioxide in amount of 10 mol percent to 300 mol percent of said alkylphenol, maintaining the temperature of the reaction mixture attemperatures of 300 F. to 390 F. at reduced pressure to remove ethyleneglycol.

4. A process of preparing a sulfurized basic alkaline earth metalcarbonated alkyl phenate comprising forming a blend comprising from 15%to 50% by weight, based on the final composition, of a lubricating oil,from 20% to 45% by weight of an alkyl phenol wherein said alkyl radicalis derived from a polypropylene having an average of 12 carbon atoms, analkaline earth metal alkyl aryl sulfonate in an amount of from 0.01 to 1mol per mol of said alkyl phenol, an aliphatic saturated monohydricalcohol having from 8 to 18 carbon atoms in an amount of from 10% to 75by weight of said alkyl phenol, heating with agitation to 180 F., andWhile maintaining the temperatures in the range of 180 to F., addingthereto a basic substance selected from the group consisting of alkalineearth metal hydroxide and alkaline earth metal oxide in amount necessaryto give a base ratio for the aforesaid carbonated alkyl phenate of from1.2 to 4.5, and a sulfur in an amount such that the mol ratio of sulfurto alkyl phenol has a value from 0.25 to 4, heating said mixture withagitation to 260 F., and, while maintaining the reaction mixture attemperatures of 260270 F., adding ethylene glycol thereto in amount suchthat. the mol ratio of basic substance to ethylene glycol is from 2:1 to0.25:1, heating said reaction mixture to a temperature of 340 F. toremove water of reaction, adding carbon dioxide at temperatures of fromabout 250 F. to about 300 F. in an amount of from 10 mol percent to 300mol percent of said alkyl phenol, followed by heating to temperatures of390 F. at reduced pressure to remove ethylene glycol and at least 50% byweight of the original charge of said monohydric alcohol.

5. A process of preparing a sulfurized basic calcium carbonated alkylphenate comprising forming a blend comprising from 20% to 30% by weight,based on the final composition, of a petroleum lubricating oil, from 25%to 35% by weight of an alkyl phenol wherein said alkyl radical isderived from a polypropylene having an average of 12 carbon atoms, acalcium alkyl aryl sulfonate in an amount of from 0.01 to 0.05 mol permol of said alkyl phenol, an aliphatic saturated monohydric alcoholhaving from 8 to 18 carbon atoms in an amount of from 10% to 50% byweight of said alkyl phenol, heating with agitation to 180 F., and Whilemaintaining temperatures of 180 to 190 F., adding thereto a basicsubstance selected from the group consisting of calcium hydroxide andcalcium oxide in amount necessary to give a base ratio for the aforesaidcarbonated alkyl 340 F., to remove water of reaction, adding carbondioxide at temperatures of from about 250 F. to about 300 F. in anamount of from 10 mol percent to 150 mol percent of said alkyl phenol,followed by heating to temperatures of 390 F. at reduced pressure toremove ethylene glycol and at least 50% by Weight of the original chargeof said alcohol.

References Cited by the Examiner UNITED STATES PATENTS 2,119,114 5/38Richardson et al 25252 2,409,687 10/46 Rogers et a1. 25242.7 2,409,72610/46 Winning et al. 25252 0 0 2,483,505 10/49 Rogers et al 252-4272,680,096 1/54 Walker et a1. 252-42.7 2,766,291 10/ 56 Weissberg et al252-42] X 3,036,971 5/62 Otto 25242.7

' FOREIGN PATENTS 727,655 4/55 Great Britain. 776,455 6/57 GreatBritain. 821,397 10/59 Great Britain.

DANIEL E. WYMAN, Primary Examiner.

JULIUS GREENWALD, Examiner.

1. A PROCESS OF PREPARING SULFURIZED BASIC ALKALINE EARTH METALCARBONATED ALKYL PENATE COMPRISING FORMING A BLEND COMPRISING APETROLEUM LUBRICATING OIL, AN ALKYL PHENOL WHEREIN SAID ALKYL RADICALHAS FROM 4 TO 30 CARBON ATOMS AND THTE TOTAL NUMBER OF CARBON ATOMS INTHE ALKYL GROUPS IS AT LEAST 8, AN ALKALINE EARTH MEAL ALKYL ARYLSULFONATE IN AN AMOUNT OF FROM 0.01 TO 1 MOL PER MOL OF SAID ALKYLPHENOL AND AN ALIPATIC SATURATED MONOHYDRIC ALCOHOL HAVING FROM 8 TO 18CARBON ATOMS IN AN AMOUNT OF FROM 10 TO 75% BY WEIGHT OF SAID ALKYLPHENOL, HEATING SAID BLEND TO TEMPERATURES N THE RANGE OF 150*F. TO190*F., ADDING THERETO A BASIC SUBSTANCE SELECTED FROM THE GROUPCONSISITNG OF ALKALINE EARTH METAL HYDROXIDE AND ALKALINE EARTH MEATALOXIDE IN AMOUNT NECESARY TO GIVE A BASE RATIO OF FROM 1.2 TO 4.5 FORSAID BASIC ALKALINE EARTH METAL CARBONATED ALKYL PHENATE, AND SULFUR INAN AMOUNT SUCH TAHT THE MOL RATIO OF SULFUR TO BASIC SUBSTANCE HAS AVALUE FROM 0.25 TO 4, HEATING SAID BLEND TO TEMPERATURES IN THE RANGE OF250*F. TO 300*F., AND AT THAT TEMPERATURE, ADDING UNHEATED ETHYLENEGLYCOL THERETO IN AMOUNT SUCH TAHT THE MOLE RATIO OF BASIC SUBSTANCE TOETHYLENE GLYCOL IS FROM ABOUT 2:1 TO ABOUT 0.25:1, REMOVING THERESULTING WATER OF REACTION BY HEATING TO TEMPERATURES OF ABOUT 340*F.,WHILE MAINTAINING TEMEPRATURES NO LOWER THAN 250*F. ADDING CARBONDIOXIDE IN AMOUNT OF 10 MOL PERCENT TO 300 MOL PERCENT OF SAID ALKYLPHENOL, MAINTAINING THE TEMPERATURE OF THE REACTION MIXTURE ATTEMPERATURES OF 300*F. TO 390*F. AT REDUCED PRESSURE TO REMOVE ETHYLENEGLYCOL.